内容

目次

About the companion website viii Chapter 1: Introduction 1 1.1 Geochemistry 1 1.2 This book 2 1.3 The philosophy of science 4 1.4 Elements, atoms, and chemical bonds: some chemical fundamentals 6 1.5 A brief look at the Earth 15 References and suggestions for further reading 19 Chapter 2: Energy, entropy and fundamental thermodynamic concepts 20 2.1 The thermodynamic perspective 20 2.2 Thermodynamic systems and equilibrium 21 2.3 Equations of state 24 2.4 Temperature, absolute zero, and the zeroth law of thermodynamics 26 2.5 Energy and the fi rst law of thermodynamics 27 2.6 The second law and entropy 30 2.7 Enthalpy 38 2.8 Heat capacity 39 2.9 The third law and absolute entropy 47 2.10 Calculating enthalpy and entropy changes 48 2.11 Free energy 51 2.12 The maxwell relations 58 References and suggestions for further reading 58 Problems 59 Chapter 3: Solutions and thermodynamics of multicomponent systems 61 3.1 Introduction 61 3.2 Phase equilibria 62 3.3 Solutions 67 3.4 Chemical potential 68 3.5 Ideal solutions 71 3.6 Real solutions 73 3.7 Electrolyte solutions 80 3.8 Ideal solutions in crystalline solids and their activities 88 3.9 Equilibrium constants 89 3.10 Practical approach to electrolyte equilibrium 96 3.11 Oxidation and reduction 100 References and suggestions for further reading 110 Problems 111 Chapter 4: Applications of thermodynamics to the Earth 116 4.1 Introduction 116 4.2 Activities in non–ideal solid solutions 116 4.3 Exsolution phenomena 120 4.4 Thermodynamics and phase diagrams 122 4.5 Geothermometry and geobarometry 128 4.6 Thermodynamic models of magmas 137 4.7 Reprise: thermodynamics of electrolyte solutions 145 References and suggestions for further reading 154 Problems 156 Chapter 5: Kinetics: the pace of things 160 5.1 Introduction 160 5.2 Reaction kinetics 161 5.3 Relationships between kinetics and thermodynamics 172 5.4 Diffusion 179 5.5 Surfaces, interfaces, and interface processes 191 5.6 Kinetics of dissolution and leaching 201 5.7 Diagenesis 207 References and suggestions for further reading 211 Problems 213 Chapter 6: Aquatic chemistry 217 6.1 Introduction 217 6.2 Acid–base reactions 217 6.3 Complexation 231 6.4 Dissolution and precipitation reactions 239 6.5 Clays and their properties 249 6.6 Mineral surfaces and their interaction with solutions 253 References and suggestions for further reading 265 Problems 265 Chapter 7: Trace elements in igneous processes 268 7.1 Introduction 268 7.2 Behavior of the elements 270 7.3 Distribution of trace elements between coexisting phases 281 7.4 Factors governing the value of partition coefficients 283 7.5 Crystal–fi eld effects 294 7.6 Trace element distribution during partial melting 299 7.7 Trace element distribution during crystallization 310 7.8 Summary of trace element variations during melting and crystallization 315 References and suggestions for further reading 316 Problems 318 Chapter 8: Radiogenic isotope geochemistry 321 8.1 Introduction 321 8.2 Physics of the nucleus and the structure of nuclei 322 8.3 Basics of radiogenic isotope geochemistry 330 8.4 Decay systems and their applications 334 8.5 Cosmogenic and fossil isotopes 360 References and suggestions for further reading 365 Problems 367 Chapter 9: Stable isotope geochemistry 371 9.1 Introduction 371 9.2 Theoretical considerations 373 9.3 Isotope geothermometry 384 9.4 Isotopic fractionation in the hydrologic system 387 9.5 Isotopic fractionation in biological systems 388 9.6 Paleoclimatology 396 9.7 Hydrothermal systems and ore deposits 404 9.8 Stable isotopes in the mantle and magmatic systems 409 9.9 Isotopes of boron and lithium 417 References and suggestions for further reading 424 Problems 428 Chapter 10: The big picture: cosmochemistry 430 10.1 Introduction 430 10.2 In the beginning . . . nucleosynthesis 431 10.3 Meteorites: essential clues to the beginning 442 10.4 Time and the isotopic composition of the solar system 456 10.5 Astronomical and theoretical constraints on solar system formation 467 10.6 Building a habitable solar system 478 References and suggestions for further reading 489 Problems 492 Chapter 11: Geochemistry of the solid earth 493 11.1 Introduction 493 11.2 The Earth’s mantle 493 11.3 Estimating mantle and bulk earth composition 502 11.4 The Earth’s core and its composition 510 11.5 Mantle geochemical reservoirs 516 11.6 The crust 529 References and suggestions for further reading 557 Problems 561 Chapter 12: Organic geochemistry, the carbon cycle, and climate 563 12.1 Introduction 563 12.2 A brief biological background 564 12.3 Organic compounds and their nomenclature 565 12.4 The chemistry of life: important biochemical processes 575 12.5 Organic matter in natural waters and soils 580 12.6 Chemical properties of organic molecules 589 12.7 Sedimentary organic matter and coal and oil formation 599 12.8 Isotope composition of hydrocarbons 614 12.9 The carbon cycle and climate 617 References and suggestions for further reading 629 Problems 633 Appendix 635 Index 637